Polyhydroxyl polyether compounds containing phosphorus and polymeric resins prepared therefrom

ABSTRACT

Polyhydroxyl polyether compounds containing at least one monomeric unit each of the formulae:   &lt;IMAGE&gt;   are disclosed. Polymeric condensation resins are prepared by allowing the polyhydroxyl polyethers to react with polyfunctional chain-forming compounds containing functional groups reactive with the hydroxyl groups of polyhydroxyl polyethers. The polyhydroxyl polyether compounds enhance the flame-retardant properties of polymeric condensation resins such as polyurethanes.

BACKGROUND OF THE INVENTION

The present invention relates generally to polyhydroxyl polyethercompounds and polymeric resins prepared therefrom.

Polymeric resins have found wide and varied use in industry. Forexample, polyurethane foams are commercially used in the fields ofinsulation, structure reinforcement, cushioning, upholstery, electricalencapsulation, and the like. Unfortunately, polymeric resins, such asthe polyurethanes, generally have very little inherent resistance toburning. In view of the extensive commercial interest in polymericresins, there have been numerous attempts to develop an effectiveflame-retardant polymeric resin.

One approach to imparting flame retardancy to polymeric resins have beento incorporate a flame-retardant additive within the resin. Illustrativeof such additives are: antimony oxide, tris(dibromopropyl)phosphate,chlorinated biphenyls, halogenated hydrocarbons, and the like. Theseadditives are not chemically bonded to the polymeric backbone of theresin, but are merely physically dispersed within the resin.Consequently, such additives have the disadvantage of being especiallysusceptible to leaching and vaporization during aging and use of thepolymeric resins.

Another approach to imparting flame retardancy to polymeric resins hasbeen to employ a reactive flame-retardant material as an integral partof the polymeric backbone. Polyhydroxyl polyether compounds containinghalogen and/or phosphorus atoms have been so used.

Such polyhydroxyl polyether compounds are a well-known class ofcompounds generally prepared by the polymerization of one or moremonomers containing an oxirane functional group ##STR2## with achain-initiating agent. Representative examples of polyhydroxylpolyether compounds which have found use in polymeric resins are: thetrichlorobutylene oxide-based polyols described in U.S. Pat. No.3,269,961; the trichloropropylene oxide-based polyols described in U.S.Pat. No. 3,402,169; the epichlorohydrin-based polyols described in U.S.Pat. Nos. 3,255,126, 4,072,638, 4,020,024 and Great Britain Pat. No.1,412,384; and the trichloroethyl phosphate-based polyols described inU.S. Pat. Nos. 3,767,732 and 3,764,640.

However, for any class of flammable material, those skilled in the arthave long been aware that some reactive flame-retardant materials aremore effective in polymeric resins than other reactive flame-retardantmaterials. This is because the efficacy of any flame retardant inpolymers or polymeric compositions is measured not only by the abilityof the material to impart flame retardancy to the polymer, but also bythe ability of the flame retardant to improve or modify, or at least notto detract from, other physical or mechanical properties of the polymeror polymeric composition.

Thus, the mere fact that a compound contains halogen and phosphorusatoms does not assure that the compound can provide usable flameretarding characteristics to the polymeric resin without substantiallyaffecting other properties of the resin. For example, the conventionalpolyhydroxyl polyether compounds described above can be used to producepolymeric resins having flame-retardant properties. However, otherphysical properties of the polymeric resins, such as humid agingcharacteristics and friability are generally adversely affected.Moreover, the formulation of the polymeric resins from conventionalpolyhydroxyl polyether compounds is rendered more difficult because ofthe predominance of terminal secondary hydroxyl groups on the polymericbackbone. These secondary hydroxyl groups are well-known in the art tobe much less reactive to the formulation of polymeric resins thanprimary hydroxyl groups.

It would therefore be desirable to provide a polyhydroxyl polyethercompound which is not only capable of imparting good flame retardingcharacteristics to a polymeric resin, but which is also capable ofinsuring commercially acceptable physical properties (e.g., humid aging,friability) in the resin. Moreover, it would be advantageous if such apolyhydroxyl polyether compound had a predominance of reactive primaryhydroxyl group incorporated within the polymeric backbone of thepolyether.

SUMMARY OF THE INVENTION

Polyhydroxyl polyether compounds having the above-describedcharacteristics have now been discovered.

The compounds have the general formula:

    R{--C.sub.2 H.sub.3 (Y)O].sub.m X}.sub.n                   (I)

where R is the residue left by the removal of n active hydrogen atomsfrom an initiator compound for alkylene oxide polymerization RH_(n) ;

Y is independently --H, --CH₃, --C₂ H₅, --CH₂ Cl, --CH₂ CCl₃, --CH₂ Br,##STR3## where Q is independently --Cl or --Br and a=1-5, or --CH₂ OXwhere X is independently --H or ##STR4## and R' and R" are eachindependently alkyl, phenyl, haloalkyl, halophenyl, alkoxy, haloalkoxy,polyhaloalkoxy, dialkylamino, diarylamino, phenoxy, halophenoxy, oralkylhalophenoxy of up to about 20 carbons; provided that at least one Yis --CH₂ OH and at least one Y is

m and n are integers such that m is at least 2, n being 1-8.

Polymeric condensation resins are also disclosed. These resins comprisethe reaction product of the polyhydroxyl polyether compounds describedabove with polyfunctional chain-forming compounds containing functionalgroups reactive with hydroxyl groups of the polyhydroxyl polyether toyield a polymeric condensation resin.

The present compounds offer numerous advantages over conventionalpolyhydroxyl polyether compounds in the preparation of polymericcondensation resins. First, due to the predominance of primary hydroxylgroups within the polymeric backbone, the present compounds exhibit anincreased reaction rate with polyfunctional chain-forming compounds.Second, the distribution of primary hydroxyl groups within the polymericbackbone of the compound can be random or specifically placed. Thisability to position primary hydroxyl groups along the polyalkylene chainbackbone creates a variety of cross-linking options. Third, the highhalogen and phosphorus atom content of the compounds allow excellentflame-retardant properties to be imparted to the polymeric resin.Fourth, the present compounds produce polymeric resins with lowerfriability than resins prepared from conventional polyols. Fifth, humidaging studies of polymeric resins produced with the compounds of thepresent invention indicate that the resins so produced exhibit superiorresistance to humid aging than resins prepared from commerciallyavailable polyhydroxyl polyether compounds. Finally, the presentcompounds are generally of lower viscosity than conventionalpolyhydroxyl polyether compounds.

DETAILED DESCRIPTION OF THE INVENTION

Compounds of formula (I) are linear polyhydroxyl polyethers containingat least one monomeric oxyalkylene unit each of the formulae: ##STR5##where R' and R" have the meaning described above.

The term "linear" as used herein, refers to each of the oxyalkylenebackbone chains --C₂ H₃ (Y)O-- attached to the initiator residue R.Obviously, if n in formula (I) exceeds 2, the molecule as a whole couldbe considered to be branched.

The oxyalkylene units have been depicted by the general formula --C₂ H₃(Y)O--. This formula corresponds to the structural isomeric formulae:##STR6##

The compounds of formula (I) are prepared from linear homopolymers orcopolymers of tert-butyl glycidyl ether (hereinafter TBGE), an epoxidehaving the structural formula: ##STR7##

The polymerization of TBGE is well-known in the art and is generallycarried out by condensing TBGE, or TBGE and one or more other cyclicether monomers, with an initiator compound in the presence of acatalyst. The preparation of polymers of TBGE is described in U.S. Pat.No. 3,519,559, which is incorporated herein by reference.

When TBGE is polymerized, the oxirane ring is opened with the breakingof an oxygen bond to form a bivalent radical oxyalkylene linkage. Ageneralized condensation polymerization reaction involving TBGE and acomonomer is illustrated by the formula: ##STR8## wherein R, Y and nhave the meaning described above and c and d are integers signifying thenumber of equivalents of comonomer or TBGE reacted for each reactivehydroxyl functionality.

To produce the compounds of formula (I), the tert-butoxy groups of TBGEpolymer of formula (V) are removed and replaced with primary hydroxygroups as shown by the generalized reaction: ##STR9## The debutylationof the t-butyl ether on the polymeric backbone can be achieved bywarming the polymer in the presence of an aryl sulfonic acid, as shownin U.S. Pat. No. 4,048,237.

In a final step, any desired proportion of the primary hydroxyl groupsof debutylated polymer of formula (VI) can be reacted with anorganophosphorus compound capable of replacing at least a portion of theprimary hydroxyl groups with a phosphate of the formula: ##STR10## whereR' and R" have the meaning described above. The generalized reaction isillustrated by the equation: ##STR11## where B is hydrogen or halogenand e is an integer equal to the number of equivalents of primaryhydroxyl groups replaced by organo phosphorus groups. In practice thetwo reactants are combined in the presence of an acid acceptor and if Bis hydrogen, preferably in a halogenated solvent, such as carbontetrachloride.

Organophosphorus compounds suitable for use include compounds of theformula: ##STR12## where B, R' and R" have the meaning described above.

The amount of the organophosphorus compound reacted with the primaryhydroxyl groups can vary depending upon the desired phosphorus contentof the final product. For example, where the polyhydroxyl polyether isemployed as a flame-retardant reactant in the preparation ofpolyurethane resins, it is desirable to provide sufficientorganophosphorus compound to produce a final polyhydroxyl polyethercompound containing from about 0.1 to about 20 percent by weightphosphorus.

A wide range of compounds containing at least one reactive hydrogen atomand having the general formula RH_(n) can be used to initiate the TBGEpolymerization reaction. The term "active hydrogen atoms" as used hereindesignates hydrogen atoms which are reactive as determined by theZerewitnoff method.

Suitable initiator compounds are those that function as initiators foralkylene oxide polymerization and have not more than 8 reactive hydrogenatoms (n=8), preferably not more than 3 reactive hydrogen atoms (n=3).Preferred initiators are polyhydroxyl compounds containing one or morehalogen or phosphorus atoms. Representative initiator compounds that maybe employed are: alkanols, such as methanol, butanol, octanol, dodecanoland octadecanol; the alkenols, such as allyl alcohol, 10-undecen-1-ol,oleyl alcohol, and the like; alkylene glycols, such as ethylene,propylene, butylene, 1,4-tetramethylene and 1,3-hexylene glycols; thehigher aliphatic polyols such as glycerol, pentaerythritol, sorbitol,sucrose, hexanetriol, alkylene oxide adducts thereof and the like;phenols, such as phenol, cresols, xylenols, hydroquinone, resorcinol,naphthols, bisphenols, and the like; aralkanols, such as benzyl alcoholand phenethyl alcohol, and the like; halogenated alcohols and polyols,such as 2-(pentachlorophenoxy)ethanol, 1,3-dibromo-2-propanol,1,3-dichloro-2-propanol, dibromoneopentyl glycol, monobromoneopentyltriol, tribromoneopentyl alcohol, 2,2,2-tribromoethanol,2,4,6-tribromophenoxyethanol, tribrominated-bis-[pentaerythritol ether],2,3-dibromo-1,4-butenediol, 2-chloro-1-ethanol, 1-chloro-2-propanol,3-chloro-1,2-propanediol, 2,3-dichloro-1-propanol,2,3-dibromo-1-propanol and the like; halogenated acids such astrichloroacetic acid, pentachlorophenoxy acetic acid and the like;halogenated pyridinols such as 3,5,6-trichloro-2-pyridinol,3,4,5,6-tetrachloro-2-pyridinol and the like. Representativephosphorus-containing hydroxyl compounds that may be employed arephosphoric acid, phosphorus acid, trichloromethyl phosphonic acid,propyl phosphonic acid, chloromethyl phosphonic acid, phenylphosphonicacid, and the like. The preferred initiator compounds are phosphoricacid, dibromoneopentyl glycol, 2,3-dibromo-1,4-butenediol, ethyleneglycol, 2-butanol, dibromopropanol, pentachlorophenoxy ethanol.

Since all practical methods for making the compounds of formula (I)involve the condensation polymerization of the initiator compounds withTBGE, one or more other cyclic ether monomers can be copolymerized withthe TBGE in this step. Suitable monomers containing an oxiranefunctionality have the generalized formula: ##STR13## Representative ofthis class of monomers are compounds wherein Y is --H (ethylene oxide),--CH₃ (1,2-propylene oxide), --C₂ H₅ (1,2-butylene oxide), --CH₂ Cl(epichlorohydrin), --CH₂ CCl₃ (trichlorobutylene oxide), --CH₂ Br(epibromohydrin), ##STR14## where Q is --Cl or --Br and a=1-5(pentachlorophenyl glycidyl ether, 2,4,6-tribromophenyl glycidyl ether),mixtures thereof, and the like. In applications wherein the compounds ofthe present invention are employed to impart flame-retardant propertiesto polymeric resins, it is preferred that TBGE be copolymerized with atleast one cyclic ether monomer containing a halogen atom. The preferredmonomers in many applications are epichlorohydrin, epibromohydrin andmixtures thereof.

The amount of monomer copolymerized with TBGE can vary depending uponthe properties desired in the final polyhydroxyl polyether product. Forexample, where the product is to be employed as a flame-retardantreactant in polymeric resins, sufficient amounts of a halogenatedmonomer are copolymerized to produce a halogen content in the finalpolyhydroxyl polyether of formula (I) sufficient to allow the polymericresin to pass a designated test for flame retardance. Preferably, thehalogen content in the polyhydroxyl polyether compound is from about 20percent to about 60 percent by weight.

The monomers may be copolymerized with TBGE in a heteric (random)fashion, wherein the monomers are reacted simultaneously, or they may bereacted to form block copolymers, wherein the monomers are reactedsequentially in any desired sequence and proportions. The number ofoxyalkylene units in the polymer chains (m in the formula (I)) may varyfrom two to many thousands, depending on the monomers and catalyst usedin its preparation.

The polyhydroxyl polyether compounds of the present invention arecharacterized by the wide range of utility common to all polyhydroxylpolyethers. However, the present compounds are particularly useful inapplications where the presence of varying amounts of halogen andphosphorus atoms and a preponderance of primary hydroxyl groups in alinear polymeric backbone are of special value. Thus, in one embodiment,the compounds of the present invention can be reacted withpolyfunctional chain-forming compounds containing functional groupsreactive with the hydroxyl groups to give a more complex polymeric resinhaving enhanced flame-retardant properties. For example, thepolyhydroxyl polyether compounds can be reacted with such polyfunctionalchain-forming compounds, as, for example, organic polyisocyanates toform polyurethanes, organic polycarboxylic acids to form polyesters,organic isocyanurates to form modified polyisocyanurates, andpolyepoxides to form higher weight polyepoxides.

The methods of preparing polymeric resins from polyfunctionalchain-forming compounds and polyhydroxyl polyether compounds arewell-known in the art. For example, a detailed description of thechemistry and technology of polyurethane, polyisocyanurate, polyesterand polyepoxide polymeric resins can be found in Encyclopedia of PolymerScience and Technology, Interscience Publishers (1971) which isincorporated herein by reference.

In one embodiment of the present invention, the polyhydroxyl polyethercompounds are employed as reactants in the production of flexible,rigid, and semi-rigid flame-retardant polyurethane foams. Suchflame-retardant foams are produced by reacting together (a) at least oneorganic polyfunctional isocyanate, (b) a flame-retardant amount of atleast one polyhydroxyl polyether of formula (I), (c) an effective amountof a polyurethane blowing agent, and (d) an effective amount of apolurethane catalyst for promoting the reaction between the organicpolyisocyanate and the polyhydroxyl polyether, are (e) a suitablesurfactant.

By the term polyfunctional isocyanate is included both monomericpolyfunctional isocyanates, such as diisocyanates, and polymericpolyisocyanates. Representative examples of organic polyfunctionalisocyanates that can be used to make the polyurethane foams include:2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, phenylenediisocyanate, 1,7-naphthylene diisocyanate, 1,5-naphthylenediisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldiisocyanate, methylene diisocyanate, trimethylene diisocyanate,tetramethylene-1,4-diisocyanate, 1,4-butylene diisocyanate, 2,3-butylenediisocyanate, 1,4-cyclohexylene diisocyanate, 1,3-cyclopentylenediisocyanate, cyclohexylene-1,2-diisocyanate,diphenyl-3,3'-dimethyl-4,7-diisocyanate, xylylene diisocyanate,cyclohexane-1,7-diisocyanate, 1-methoxyphenyl-2,4-diisocyanate,1,2,4-benzene triisocyanate, polymethylene polyphenylisocyanate,tolylene-2,4,6-triisocyanate, 4,7'-dimethyldiphenylmethane-2,2',5,5'-tetraisocyanate, 7,4'-biphenylene diisocyanate,triphenylmethane-7,4',4"-triisocyanate, cumylene 2,4-diisocyanate,durylene diisocyanate, 2,4-diphenylhexane-1,6-diisocyanate,2-chlorotrimethylene diisocyanate, diphenyl-2,4,4-triisocyanate,dodecane-1,12-diisocyanate, cyclobutane-1,3-diisocyanate,hexahydrotolylene-2,4-diisocyanate,1-methyl-2,4-diisocyanatocyclohexane, mixtures and polymers thereof, andthe like.

By employing polyhydroxyl polyethers of the invention having variousdegrees of functionality in combination with polyfunctional isocyanatesof varied functionality, foams having any desired amount of flexibilityranging from flexible, semi-flexible to rigid may be produced.

The amount of polyfunctional isocyanate employed in the preparation ofthe polyurethane foams should be sufficient to provide at least 0.7 NCOgroups based on the number of hydroxyl groups present in thepolyhydroxyl polyether component and any other component. An excess ofthe polyfunctional isocyanate can be employed. However, this isgenerally limited due to the high cost of the polyfunctional isocyanatecomponent. It is preferable, therefore, to employ no greater than 2.0NCO groups based on the number of hydroxyl groups and preferably betweenabout 0.9 to 1.2 NCO groups.

A catalyst for the reaction between the polyfunctional isocyanate andthe polyhydroxyl polyether compounds is usually desirable when cellularpolyurethane foams are produced. The catalyst employed can be any of thecatalysts known to be useful for this purpose, including tertiary aminesand metallic salts. Representative examples of suitable catalystsinclude: triethylene diamine, dibutyltin dilaurate, triethylamine,N,N-dimethylcyclohexylamine, cobalt naphthenate, stannous octoate,N-methyl morpholine, N-hydroxyethyl morpholine, and the like. Generally,the catalyst is employed in an amount of from about 0.01 to about 5percent by weight based on the total polyol content of the reactionmixture.

The blowing agent employed in preparing the polyurethane foams can beany of those known to be useful for this purpose, such as aliphatichydrocarbons boiling below 110° C. or halogenated aliphatichydrocarbons, boiling below 110° C., and mixtures thereof. Typicalhalogenated hydrocarbons include the following:monofluorotrichloromethane, difluorodichloromethane,1,1,2-trichloro-1,2,2-trifluoroethane, methylene chloride, chloroform,hexane, hexene, pentane, carbon tetrachloride, and the like. The choiceof blowing agent is influenced by the type of polyurethane foam which isdesired. For example, methylene chloride is a suitable blowing agent forflexible polyurethane foams but is not suitable for rigid polyurethanefoams since the latter are solubilized by methylene chloride. Someblowing agents such as difluorodichloromethane are suitable for eitherflexible or rigid polyurethane foams. Suitable blowing agents aredisclosed in U.S. Pat. No. 3,072,582. The amount of the foaming agentemployed may be varied within a wide range depending upon the propertiesdesired in the foam. Generally, however, the blowing agent is employedin an amount of from about 10 to about 50 parts by weight of thepolymeric formulation.

It is preferred in the preparation of polyurethane foams to employ minoramounts of a surfactant in order to improve the cell structure of theresulting foam. Illustrative of such surfactants are polypropyleneglycols having molecular weights between 2000 and 8000, the liquidsilicone-glycol copolymers having viscosities of from 350 to 3500centistokes at 77° F. and polysiloxane polyoxyalkylene block copolymersas described in U.S. Pat. No. 2,834,748.

If desired, cell-size control agents, synergists such as antimony oxide,fillers, pigments, emulsifiers, water, inhibitors against discolorationand aging, and other additives can also be added to the urethanereaction mixture.

Additional polyfunctional hydroxyl compounds can be employed tosupplement the polyhydroxyl polyether compounds as reactant in formingpolyurethanes. Suitable polyfunctional hydroxyl compounds for use in themanufacture of polyurethanes include glycols, triols, hexols, octols,polyester polyols, and polyether polyols. Illustrative of such compoundsare the alkylene oxide adducts of water or any of the followingpolyhydroxy-containing organic compounds: ethylene glycol, diethyleneglycol, propylene glycol, dipropylene glycol, trimethylene glycol,butylene glycols, glycerine, 1,2,6-hexanetriol, 1,1,1-methyolethane,1,1,1-trimethyolpropane, 3-(2-hydroxyethoxy)-1,2-propanediol,pentaerythritol, 1,2-cyclohexanediol, fructose, sorbitol, sucrose,lactose, glycosides, resorcinol, pyrogallol, phloroglucinol, di-, tri-and tetra-phenylol, alkanol amines, higher alkylene oxide adducts of theforegoing and the like.

The amount of the flame-retardant polyhydroxyl polyether compound ofthis invention which is incorporated into any particular polyurethanereaction mixture depends on several factors including the degree offlame retardancy desired, whether an additional flame retardant isemployed, the chemical composition of the polyurethane material, thephysical nature (i.e., cellular or non-cellular), the density, and withrespect to cellular polymers, the nature of the cellular structure(i.e., flexible, semi-flexible or rigid).

It is recognized, however, that all known organic polymers will burnwhen subjected to a sufficiently intense heat source. Thus, terms suchas "flame retardant" and "flame spread rating" are not intended toindicate performance under actual fire conditions.

The urethane polymerization reaction can be conducted by any of thethree principal reaction methods: (a) prepolymer; (b) semi- orquasi-prepolymer; and (c) one-shot. In the "one-shot" procedure, thepolyhydroxyl polyether compound, the organic polyfunctional isocyanate,and other components (i.e., additional polyfunctional hydroxylcompounds, catalyst, blowing and surfactant agents) are mixedsimultaneously. In the prepolymer method, the polyhydroxyl polyethercompound, and optionally other polyfunctional hydroxyl compounds aremixed with an excess of the organic polyfunctional isocyanate before theother components are added. In the semi- or quasi-prepolymer method, theorganic polyfunctional isocyanate is reacted with a portion of thepolyhydroxyl polyether compound and optionally with a portion of anyother polyfunctional hydroxyl compound, producing a low molecular weightpolymer of low viscosity. This semi-polymer is then reacted with theremainder of the polyhydroxyl polyether compound and optionally with theremainder of any additional polyfunctional hydroxyl compound.

The polyurethane polymeric compositions produced can be made into usefularticles by conventional molding, casting, coating, and laminatingtechniques, all of which are well-known in the art.

In a manner substantially identical to that used to produce polyurethanefoams, the polyhydroxyl polyether compounds of the present invention canbe employed as reactants in the production of flame-retardantpolyisocyanurate foams. Such foams are produced by reacting together (a)at least one organic polyisocyanate, (b) a flame-retardant amount of atleast one polyhydroxyl polyether of formula (I), (c) an effective amountof a polyisocyanurate blowing agent, (d) an effective amount of anisocyanate-trimerization catalyst, and optionally (e) a surfactant.

Any of the organic polyisocyanates, blowing agents and surfactantsemployed in the preparation of the polyurethane foams can be used in thepreparation of the polyisocyanurate foams.

The isocyanurate-trimerization catalysts used in the preparation ofpolyisocyanurates are compounds which have a catalytic activity fortrimerizing isocyanate groups. Typical isocyanate-trimerizationcatalysts include: (a) tertiary amines such as triethylamine,N,N',N"-tris(dimethylaminopropyl)hexahydrotriazine,2,4,6-tris(dimethylaminomethyl)phenol, tetramethyl ethylenediamine; (b)mixtures of the tertiary amine and a promoter, such as ethanol,mono-N-substituted carbamic acid esters, water, aliphatic aldehydes,tertiary amines, benzoyl peroxide, ethylenecarbonate, α-diketones (e.g.,diacetyl) and various epoxy compounds; (c) tertiary phosphines such astriethyl phosphine; (d) alkali metal salts of imides such as potassiumphthalimide and sodium succinimide; (e) organic onium compounds such astetraethyl ammonium hydroxide, benzyl triethylammonium hydroxide,tetraethyl phosphonium hydroxide, trimethyl sulfonium hydroxide; (f)ethyleneimines such as N-butyl ethyleneimine and 2-hydroxyethylethyleneimine; (g) metal salts of carboxylic acid such as potassiumacetate, potassium 2-ethylhexanoate, lead 2-ethylhexanoate, sodiumbenzoate, potassium naphthenate and tin octanoate; (h) basic inorganiccompounds such as potassium carbonate, calcium hydroxide, barium oxide,potassium hydroxide and sodium hydroxide; (i) alcolates and phenolatessuch as sodium methoxide, potassium phenolate and sodiumtrichlorophenolate; (j) Ti- and Sb-compounds such as tetra-butyltitanate and tri-n-butyl antimony oxide; (k) Friedel-Crafts catalystssuch as zinc chloride, tin chloride, ferric chloride, antimonypentachloride, aluminum chloride and borontrifluoride; (1) alkali metalcomplexes such as alkali metal complexes of salicylaldehyde,acetylacetone, o-hydroxyacetophenone or quinizarine and alkali metalcomplexes of tetra-valent boron compounds.

The amount of the polyisocyanate employed in the preparation of thepolyisocyanurate foams should be sufficient to provide at least about1.5 NCO groups based on the number of hydroxyl groups present in thepolyhydroxyl polyether component and any other component. An excess ofthe polyisocyanate can be employed up to about 15 isocyanate equivalentsfor each hydroxyl equivalent. However, it is preferable to employ fromabout 2.0 to about 6.0 NCO groups based on the number of hydroxy groups.

In another embodiment of the present invention, the polyhydroxylpolyether compounds are employed as reactants in the production offlame-retardant saturated and unsaturated polyesters. Suchflame-retardant foams are produced by reacting together (a) at least onesaturated or unsaturated organic polycarboxylic component and (b) aflame-retardant amount of at least one polyhydroxyl polyether of formula(I).

Any saturated or unsaturated organic polycarboxylic compound can beemployed in the preparation of the polyester. By organic polycarboxyliccompound is meant the organic polycarboxylic acids, organicpolycarboxylic anhydrides, organic polycarboxylic acid halides, andorganic polycarboxylic acid esters. Suitable unsaturated polycarboxylicacids having aliphatic carbon-to-carbon double bonds, and thecorresponding acid halides, esters, and anhydrides can include maleic,fumaric, chloromaleic, ethylmaleic, itaconic, citraconic, zeronic,pyrocinchoninic, mesaconic, aconitic and acetylene dicarboxylic, eitheralone or in mixtures. The saturated polycarboxylic compounds useful inthe preparation of the polyesters can be aliphatic, cycloaliphatic,aromatic or heterocyclic. Illustrative of these polycarboxylic acids,acid halides, acid anhydrides and acid esters include phthalic,isophthalic, terephthalic, tetrachlorophthalic, tetrabromophthalic,dibromotetrahydrophthalic, chlorendic, adipic, succinic,dichlorosuccinic and mixtures thereof.

When an unsaturated anhydride such as maleic anhydride is used, anunsaturated polyester is produced which contains polymerizable doublebonds. Curing by copolymerization of a reactive, volatile monomer suchas styrene with the unsaturated polyester results in a three dimensionalrigid network. In addition to styrene, a variety of ethylenicallyunsaturated monomers such as methyl methacrylate, vinyl toluene,α-methyl styrene, divinyl benzene, the halogenated styrenes, diallylphthalate, triallyl cyanurate or mixtures of the above may be used.Additional monomers are also listed on page 30, Table II-1.7 in"Handbook of Reinforced Plastics" 1964, S. S. Oleesky and G. Mohr,Reinhold Publishing Corp., New York. The particular choice of monomerand the specific composition of the unsaturated polyester are dependenton the properties ultimately desired in the cured article and are knownor readily determined by those skilled in the art. Additional valuableinformation useful in selecting the resin and monomer can also be foundon pages 13-55 in the above reference.

In yet another embodiment of the present invention, the polyhydroxylpolyether compounds can be employed in the synthesis of higher molecularweight epoxy resins by reacting (a) at least one polyepoxide; (b) atleast one polyhydroxyl polyether of formula (I); and (c) a suitablecatalyst. The synthesis of such higher-molecular weight polyepoxides isdescribed, for example, in Handbook of Epoxy Resins, H. Lee, K. Neville,McGraw-Hill Book Company, New York 1967, pages 2-6 to 2-9, whichreference is incorporated herein by reference.

The invention has been described in detail with particular reference tocertain preferred embodiments thereof, but it will be understood thatvariations and modifications can be effected within the spirit and scopeof the invention.

The invention is further illustrated by the following examples.

Example 1

Part A--Preparation of TBGE-Epichlorohydrin Copolymer

Monomeric tert-butyl glycidyl ether (TBGE) was copolymerized withepichlorohydrin using 2,3-dibromo-1,4-butenediol to initiate the polymerchain. The reaction was conducted in a two-liter, three-necked flaskequipped with a stirrer and reflux condenser. Into the flask were placed500 milliliters (ml) of methylene chloride, 105 grams (g) of2,3-dibromo-1,4-butenediol (0.4 mole), and 3 ml boron trifluorideetherate. The resulting mixture was stirred and heated to reflux. Asolution of 474 g epichlorohydrin (5.12 moles) and 224 g TBGE (1.72moles) was then added to the refluxing mixture at a sufficient rate tomaintain a gentle reflux.

The resulting reaction mixture was stirred at reflux until all the TBGEand epichlorohydrin had reacted, thus assuring that the molarproportions of each component in the product were the same as in thereactor feed.

The completion of the reaction was determined by the "epoxy test". Inthis test, 2 ml of the reaction mixture were added to 10 ml of an aceticacid solution containing 20 percent by weight tetraethylammoniumbromide. Five drops of 1 percent by weight crystal violet dissolved in 1g of acetic acid was added to the test solution. When the test solutionturned green, the reaction was complete.

Part B--Dealkylation of the TBGE-Epichlorohydrin Copolymer

When the reaction described in Part A was complete, 3 g ofp-toluenesulfonic acid hydrate were added to the reaction mixture. Themixture was then heated at about 130° C. until dealkylation of thet-butyl moiety was complete. The mixture was allowed to cool to roomtemperature and then 700 ml of methylene chloride and 500 ml of anaqueous NaOH solution were added. The resulting product layer wasseparated. The polymeric product was essentially free of t-butyl groupsas demonstrated by nuclear magnetic resonance spectroscopy (NMR).

Part C-Reaction of TBGE-Epichlorohydrin Copolymers With OrganophosphorusCompound

A 165 g (0.1 mole) portion of the TBGE-epichlorohydrin copolymer of PartB was mixed with 50 ml carbon tetrachloride, 400 ml methylene chloride,15 g (0.1 mole) diethyl hydrogen phosphite, and 15 g (0.1 mole)triethylamine in a 1-liter flask. The resulting mixture was stirred atreflux for about 8 hours. After 8 hours, the mixture was cooled andmixed with 200 ml of water. The product layer was then separated, driedover sodium sulfate, filtered, and distilled at 60° C. under reducedpressure to remove solvent. About 179 g of product (95 percent yield)was isolated. NMR analysis showed complete reaction of the diethylhydrogen phosphite.

The principal properties of the polyhydroxyl polyether product obtainedare shown in Table I.

EXAMPLES 2-7

In a manner substantially as described in

Example 1, the polyhydroxyl polyethers described in Table I wereprepared.

                                      TABLE I                                     __________________________________________________________________________    Reactants                                                                                   Molar/   OH  Product    Viscosity                               Example                                                                            Component                                                                              Ratio                                                                             Mol Wt                                                                             Funct                                                                             % Cl                                                                              % Br                                                                              % P                                                                              (77° F.)CPS                                                                   n m                              __________________________________________________________________________         Di Br Butenediol                                                                       1                                                               1    Epi-Cl   12                                                                   TBGE     4   1789 5   23.8                                                                               8.9                                                                              1.7                                                                              54,000 2 16                                  DEHP     1                                                                    Dipentek 1                                                               2    Epi-Cl   12                                                                   TBGE     2   1838 4   23.0                                                                              13.0                                                                              1.7                                                                              --     2 14                                  DEHP     1                                                                    PCl PEtOH                                                                              1                                                               3    Epi-Cl   12                                                                   TBGE     4   1853 4   32.6                                                                              --  1.7                                                                              --     1 16                                  DEHP     1                                                                    MeOH     1                                                               4    Epi-Cl   12                                                                   TBGE     4   1574 4   27.0                                                                              --  2.0                                                                              --     1 16                                  DEHP     1                                                                    MeOH     1                                                               5    Epi-Cl   12                                                                   TBGE     5   1826 4   23.3                                                                              --  3.4                                                                              --     1 17                                  DEHP     2                                                                    DBNPG    1                                                               6    Epi-Cl   12                                                                   TBGE     4   1793 5   23.8                                                                               8.9                                                                              1.7                                                                              75,000 2 16                                  DEHP     1                                                                    Phosphoric Acid                                                                        1                                                               7    Epi-Cl   12                                                                   TBGE     2   1492 4   28.6                                                                              --  4.2                                                                              45,000 3 14                                  DEHP     1                                                               __________________________________________________________________________     Note:                                                                         MeOH = methanol                                                               EpiCl = epichlorohydrin                                                       TBGE = tertbutyl glycidyl ether                                               DEHP = diethylphosphonate                                                     PCl PEtOH = pentachlorophenoxyethanol                                         Di Pentek = tribrominatedbis[pentaerythritol                                  Di Br Butenediol = 2,3dibromo-1,4-butenediol                                  DBNPG = dibromoneopentyl glycol                                          

EXAMPLE 8 Preparation of Polyurethane Resin Composition

Using the polyhydroxyl polyether compound prepared in Example 1, Part C,a polyurethane foam was prepared by adding an organic polyisocyanate toa well stirred mixture of the polyhydroxyl polyether and the otherreaction components described in Table II, Part A. The resulting mixturewas mechanically stirred for about 10 seconds, and then was poured intoa cyclindrical container prior to the reaction cream time. The foam wasthen allowed to cure at ambient temperature.

The resulting foam was subjected to the West German DIN 4102-B2 test for"Behavior of Building Materials and Components in Fire; BuildingMaterials; Definitions, Requirement and Test". The physical propertiesof the polyurethane foams were measured by conventional methods. Thephysical properties of the foam and DIN 4102 test results are describedin Table II, Part B.

                  TABLE II                                                        ______________________________________                                        Part A - Resin Formulation                                                    Component                Example 1                                            ______________________________________                                        F. R. Polyol             15.0 g                                               Polyhydroxy (a)          85.0 g                                               Tin-based Catalyst (b)   0.2 g                                                Amine Catalyst (c)       1.0 g                                                Blowing Agent (d)        38.0 g                                               Polyisocyanate (e)       124.0 g                                              ______________________________________                                        Part B - Properties of Resin                                                  Property                 Example 1                                            ______________________________________                                        Cream Time (sec)         12.0                                                 String Time (sec)        29.0                                                 Tack-free Time (sec)     45.0                                                 Density (lb/ft3)         2.0                                                  Humid Aging (% Volume Change)                                                                          10.7                                                 (28 Days, 70° C. 100% R.H.)                                            Compressive Strength ASTM D-1621-64                                           parallel to foam rise (psi)                                                                            9.9                                                  perpendicular to foam rise (psi)                                                                       36.4                                                 Flammability Test        Passed                                               (DIN 4102-B2)                                                                 Friability (%) ASTM C-3421-61                                                                          7.8                                                  Insulating (K) Factor ASTM C-1777-71                                                                   0.138                                                ______________________________________                                         Notes                                                                         (a) a blend of 50 parts by weight of an ethylenediamine-initiated             propylene oxide polymer having hydroxyl number 640 and functionality of       4.0 and 50 parts by weight of a sucrose/glycerineinitiated propylene oxid     polymer having a hydroxyl number of 456 and a functionality of 4.7.           (b) T131  a stannous catalyst, M&T Chemicals Inc., Woodbridge Avenue,         Rahway, N.J.                                                                  (c) Polycat® 8  dimethylcyclohexylamine, Abbot Laboratories, Chicago,     Ill.                                                                          (d) Freon® 11  trichlorofluoromethane, E.I. du Pont de Nemours & Co.,     Wilmington, Del.                                                              (e) Mondur® MR  a diphenyl methane diisocyanate, Mobay Chemical Co.,      Pittsburgh, PA.                                                          

EXAMPLE 9

The reaction conditions of Example 8 were repeated excepting thatvarious amounts of the phosphorus-containing polyhydroxy polyetherspreviously formed were used in the formulation and an additionalphosphorus-containing compound was physically incorporated into the foamby adding dimethyl methylphosphonate to the reaction mixture. A controlfoam containing no phosphorus-containing polyhydroxy polyether was alsotested. Results are contained in Table III.

                  TABLE III                                                       ______________________________________                                                        %                                                                    % of     Extra            Vertical                                                                              %                                    Poly-  Total    P        Density Burn    Humid                                ether  polyol   Added.sup.1                                                                            (kg/m.sup.3)                                                                          (cm/min).sup.2                                                                        Age.sup.3                            ______________________________________                                        Ex. 1  20       --       32.8    --      13.8                                        15       --       28.5    --      4.9                                  Ex. 2  15       --       33.3    24.1    --                                   Ex. 6  20       --       27.2    28.9    --                                          20       2        29.0    24.6    --                                          15       --       27.9    24.9    6.6                                  Ex. 7  20       --       30.1    26.9    4.9                                         50       --       31.2    19.1    --                                   Control                                                                               0       --       32.0    33.0    3.1                                  ______________________________________                                         .sup.1 Weight percent of dimethyl methylphosphonate based on                  phosphoruscontaining polyhydroxy polyether.                                   .sup.2 A small foam sample 7/8in × 1/2in × 3 in (2.2 cm           × 0.63 cm × 7.6 cm) is ignited in a controlled atmosphere (25     O.sub.2). The amount of time 1/4 for the foam to burn 2 inches (5.1 cm) i     recorded. The rate is then calculated.                                        .sup.3 % volume change after 28 days, 70°  C., 100% relative           humidity.                                                                

What is claimed is:
 1. A polymeric condensation resin comprising thereaction product of:(a) at least one polyhydroxyl polyether of theformula

    R{C.sub.2 H.sub.3 (Y)O.sub.m X}.sub.n

where R is the residue left by the removal of n active hydrogen atomsfrom an initiator compound for alkylene oxide polymerization RH_(n) ; Yis independently --H, --CH₃, --C₂ H₅, --CH₂ Cl, --CH₂ CCl₃, --CH₂ Br,##STR15## where Q is independently --Cl or --Br and a=1-5, or --CH₂ OXwhere X is independently --H or ##STR16## and R' and R" are eachindependently alkyl, phenyl, haloalkyl, halophenyl, alkoxy, haloalkoxy,polyhaloalkoxy, polyhalophenoxy alkoxy, dialkylamino, arylamino,halophenoxy, or alkylhalophenoxy of up to about 20 carbons; providedthat at least one Y is --CH₂ OH and at least one Y is ##STR17## and mand n are integers such that m is at least 2, n being 1-8; and (b) apolyfunctional chain-forming compound containing functional groupsreactive with hydroxyl groups of the polyhydroxyl polyether to yield thepolymeric condensation resin.
 2. The polymeric resin of claim 1 whereinthe polyfunctional chain-forming compound of part (b) is selected fromthe group consisting of organic polyfunctional isocyanates, organicpolycarboxylic acids, organic polyfunctional isocyanurates, and organicpolyepoxides.
 3. The polymeric resin of claim 1 comprising the reactionproduct of:(a) at least one organic polyisocyanate; (b) at least onepolyhydroxyl polyether of (a); (c) an effective amount of a polyurethaneblowing agent; (g) an effective amount of a polyurethane catalyst forpromoting the reaction between said organic polyisocyanate and saidpolyhydroxyl polyether; and (e) a suitable polyurethane surfactant. 4.The polymeric resin of claim 3 wherein said organic polyfunctionalisocyanate is used in amounts corresponding to at least 0.7 NCO groupsfor each reactive hydroxyl group present in the mixture of reactivematerials.
 5. The polymeric resin of claim 1 comprising the reactionproduct of:(a) at least one organic polyisocyanate; (b) at least onepolyhydroxyl polyether of (a); (c) an effective amount of apolyisocyanurate blowing agent; and (d) an effective amount of anisocyanate-trimerization catalyst for promoting the trimerizing of theisocyanate groups.